Process for preparing acrylate compound

ABSTRACT

An acrylate compound of formula (4):  
                 
 
     is produced by allowing an acrylic acid compound of formula (1):  
                 
 
     to react with an unsaturated compound of formula (2) or (3):  
                 
 
     In formulae (1) through (4), R 1  and R 2  are H or F, R 3  is H, F, or an alkyl, alkenyl, fluoroalkyl or fluoroalkenyl group, R 4  and R 5  are H, halogen, or an alkyl, alkenyl, halogenated alkyl or halogenated alkenyl group; and X and Y are an unsubstituted or substituted hydrocarbon group, and dashed line - - - - - means that X and Y may be bonded together to form a cyclic structure.

BACKGROUND OF THE INVENTION

[0001] (1) Field of the Invention

[0002] This invention relates to a process for preparing an acrylatecompound which is expected to be used as a raw material for functionalpolymers, pharmaceuticals and pesticides.

[0003] (2) Description of the Related Art

[0004] In recent years acrylate compounds have provided a greatattraction, for example, as monomers used for producing a resist foradvanced semiconductor lithography. Especially acrylate compounds havinga tertiary ester skeletal structure capable of being dissociated with anacid are suitable therefor in view of lithography mechanism.

[0005] As specific examples of the acrylate or methacrylate compoundshaving such a skeletal structure capable of being dissociated with anacid, there can be mentioned acrylates and methacrylates having anacid-dissociatable group such as a 2-methyl-2-adamantyl group or a8-ethyl-8-tricyclodecanyl group (Japanese Unexamined Patent Publication[hereinafter abbreviated to “JP-A”) No. 2001-188352, JP-A H11-305444 andJP-A H9-43848), and α-trifluoromethylacrylates having anacid-dissociatable group such as a 2-methyl-2-adamantyl group or a1-alkyl-1-cycloalkyl group (JP-A 2001-302728).

[0006] The above-mentioned acrylate compounds are prepared, for example,by the following known processes.

[0007] A first type process comprises allowing an acrylic acid chloridecompound to react with an alcohol or a metal alcoholate in the presenceof a base. The first type process includes, for example, a processwherein 2-methyl-2-adamantanol is allowed to react with acryloylchloride or methacryloyl chloride in the presence of triethylamine togive a corresponding acrylate or methacrylate compound (for example,JP-A H11-305444, JP-A 2000-122294, JP-A 2000-229911 and JP-A2001-188352), and a process wherein 8-ethyl-8-cyclododecanol is allowedto react with methacryloyl chloride in the presence of triethylamine(JP-A 2001-188352). The first type process further includes a processwherein 2-adamantanone is allowed to react with methyllithium or amethyl Grignard reagent to give a Li or Mg salt of2-methyl-2-adamantanonol, and then, methacryloyl chloride is added in asolution of the thus-obtained Li or Mg salt to give a correspondingmethacrylate compound (JP-A H10-182552 and JP-A 2000-229911).

[0008] The first type process has a problem such that acryloyl chlorideand methacryloyl chloride are not readily available and are expensive,and are difficult to handle because these acid chlorides easily producea large amount of hydrogen chloride gas when they are contacted withmoisture in the air.

[0009] As a process wherein acryloyl chloride and methacryloyl chlorideare not used to overcome the first type process, a second process hasbeen proposed which includes, for example, a process wherein acrylicacid is allowed to react with a tertiary alcohol such as1-ethyl-1-cyclohexanol (JP-A 2000-319226).

[0010] However, in the second process, large amounts of a carboxylicacid anhydride such as acetic anhydride and an amine compound such astriethylamine must be used to smoothly carry out the reaction, with theresult of reduction in efficiency and cost for production.

SUMMARY OF THE INVENTION

[0011] In view of the foregoing, a primary object of the presentinvention is to provide a process for preparing acrylate compoundswhereby the object compounds can be prepared with high efficiencywithout the above-mentioned problems of the prior art, namely, with areduced cost and an enhanced safety.

[0012] Thus, in accordance with the present invention, there is provideda process for preparing an acrylate compound represented by thefollowing formula (4):

[0013] wherein R¹ and R² independently represent a hydrogen atom or afluorine atom, R³ represents a hydrogen atom, a fluorine atom, an alkylgroup, an alkenyl group, a fluoroalkyl group, or a fluoroalkenyl group,R⁴ and R⁵ independently represent a hydrogen atom, a halogen atom, analkyl group, an alkenyl group, a halogenated alkyl group, or ahalogenated alkenyl group; and X and Y independently represent ahydrocarbon group, which may have at least one substituent selected fromthe group consisting of a halogen-containing substituent, anoxygen-containing substituent and a nitrogen-containing substituent, anddashed line - - - - - means that X and Y may be bonded together to forma cyclic structure;

[0014] which comprises allowing an acrylic acid compound represented bythe following formula (1):

[0015] wherein R¹, R² and R³ are the same as defined above for formula(4), to react with an unsaturated compound represented by the followingformula (2) or (3):

[0016] wherein R⁴, R⁵, X and Y are the same as defined above for formula(4).

DESCRIPTION OF THE PREFERRED EMBODIMENT

[0017] The acrylic acid compound used as a raw material in the processof the present invention is represented by the above formula (1). Informula (1), R¹ and R² independently represent a hydrogen atom or afluorine atom, and preferably represent a hydrogen atom.

[0018] In formula (1), R³ represents a hydrogen atom, a fluorine atom,an alkyl group, an alkenyl group, a fluoroalkyl group or a fluoroalkenylgroup. R³ is preferably selected from a hydrogen atom, a fluorine atom,a C₁-C₄ straight-chain or branched alkyl group, a C₂-C₄ straight-chainor branched alkenyl group, a C₁-C₄ straight-chain or branchedfluoroalkyl group, and a C₂-C₄ straight-chain or branched fluoroalkenylgroup. As specific examples of the alkyl group, there can be mentionedmethyl, ethyl, propyl and butyl groups. As specific examples of thealkenyl group, there can be mentioned ethenyl, 1-propenyl, allyl and 1-,2- or 3-butenyl groups. As specific examples of the fluoroalkyl group,there can be mentioned fluoromethyl, fluoroethyl, fluoropropyl andfluorobutyl groups. As specific examples of the fluoroalkenyl group,there can be mentioned fluoroethenyl, fluoro-1-propenyl, fluoroallyl andfluoro-1-butenyl, fluoro-2-butenyl and fluoro-3-butenyl groups.

[0019] Preferable examples of the acrylic acid compound of formula (1)are those wherein R¹ and R² are a hydrogen atom, and R³ is selected froma hydrogen atom, a fluorine atom, an alkyl group (preferably a C₁-C₄straight-chain or branched alkyl group), an alkenyl group (preferably aC₂-C₄ straight-chain or branched alkenyl group), a fluoroalkyl group(preferably a C₁-C₄ straight-chain or branched fluoroalkyl group) and afluoroalkenyl group (preferably a C₂-C₄ straight-chain or branchedfluoroalkenyl group).

[0020] As specific examples of the acrylic acid compound, there can bementioned acrylic acid, methacrylic acid, α-ethylacrylic acid,α-n-propylacrylic acid, α-isopropylacrylic acid, α-n-butylacrylic acid,α-isobutylacrylic acid, α-s-butylacrylic acid, α-allylacrylic acid,α-t-butylacrylic acid, α-fluoromethylacrylic acid,α-trifluoromethylacrylic acid, α-fluoroacrylic acid, α-difluoroacrylicacid, α-trifluoroacrylic acid, α-fluoroethylacrylic acid,α-difluoroethylacrylic acid, α-trifluoroethylacrylic acid,α-tetrafluoroethylacrylic acid, α-perfluoroethylacrylic acid,α-fluoropropylacrylic acid, α-difluoropropylacrylic acid,α-trifluoropropylacrylic acid, α-tetrafluoropropylacrylic acid,α-pentafluoropropylacrylic acid, α-hexafluoropropylacrylic acid,α-perfluoropropylacrylic acid, α-fluorobutylacrylic acid,α-difluorobutylacrylic acid, α-trifluorobutylacrylic acid,α-tetrafluorobutylacrylic acid, α-pentafluorobutylacrylic acid,α-hexafluorobutylacrylic acid, α-heptafluorobutylacrylic acid,α-octafluorobutylacrylic acid, α-perfluorobutylacrylicacid,α-fluoroallylacrylic acid, α-difluoroallylacrylic acid,α-trifluoroallylacrylic acid, α-tetrafluoroallylacrylic acid,α-perfluoroallylacrylic acid, α-trifluoromethyl-β-fluoroacrylic acid,α-trifluoromethyl-β,β-difluoroacrylic acid and α,β,β-trifluoroacrylicacid.

[0021] Of these, α-trifluoromethylacrylic acid, α-trifluoroethylacrylicacid, α-perfluoroethylacrylic acid, α-perfluoropropylacrylic acid,α-perfluorobutylacrylic acid, α-fluoroacrylic acid, acrylic acid andmethacrylic acid are preferable. α-trifluoromethylacrylic acid, acrylicacid and methacrylic acid are especially preferable.

[0022] The unsaturated compound used as a raw material in the process ofthe present invention is represented by the formula (2) or (3), whichhas at least one carbon-carbon double bond in the structure and at leastone carbon atom of the carbon-carbon double bond is bonded to onlycarbon atoms, namely, is not directly bonded to any atom other thancarbon atom. The skeleton of the unsaturated compound may be either achain-like structure including a straight chain structure and a branchedstructure, or an alicyclic structure.

[0023] The above-mentioned unsaturated compound of formula (2) or (4)includes, for example, those which are represented by the followingformulae (7) through (13).

[0024] Compounds represented by the following formula (7):

[0025] wherein R⁷ and R⁸ independently represent a hydrogen atom, ahalogen atom, a C₁-C₄ straight-chain or branched alkyl group, a C₂-C₄straight-chain or branched alkenyl group, a C₁-C₄ straight-chain orbranched haloalkyl group, or a C₂-C₄ straight-chain or branchedhaloalkenyl group, and R⁹ and R¹⁰ independently represent a C₁-C₁₀straight-chain or branched alkyl group, or a C₂-C₁₀ straight-chain orbranched alkenyl group;

[0026] compounds represented by the following formula (8):

[0027] wherein R⁷ and R⁸ independently represent a hydrogen atom, ahalogen atom, a C₁-C₄ straight-chain or branched alkyl group, a C₂-C₄straight-chain or branched alkenyl group, a C₁-C₄ straight-chain orbranched haloalkyl group, or a C₂-C₄ straight-chain or branchedhaloalkenyl group, and R¹¹ and R¹² independently represent a C₁-C₁₀straight-chain or branched alkyl group, or a C₂-C₁₀ straight-chain orbranched alkenyl group;

[0028] compounds represented by the following formula (9):

[0029] wherein R⁷ and R⁸ independently represent a hydrogen atom, ahalogen atom, a C₁-C₄ straight chain or branched alkyl group, a C₂-C₄straight chain or branched alkenyl group, a C₁-C₄ straight-chain orbranched haloalkyl group, or a C₂-C₄ straight-chain or branchedhaloalkenyl group, and R¹³ represents a C₂-C₁₅ straight chain orbranched alkylene group or a C₂-C₁₅ straight-chain or branchedalkenylene group;

[0030] compounds represented by the following formula (10):

[0031] wherein R⁷ and R⁸ independently represent a hydrogen atom, ahalogen atom, a C₁-C₄ straight-chain or branched alkyl group, a C₂-C₄straight-chain or branched alkenyl group, a C₁-C₄ straight-chain orbranched haloalkyl group, or a C₂-C₄ straight-chain or branchedhaloalkenyl group, and R¹⁴ represents a C₁-C₁₅ alkylene group, or aC₂-C₁₅ alkenylene group;

[0032] compounds represented by the following formula (11):

[0033] wherein R⁷ and R⁸ independently represent a hydrogen atom, ahalogen atom, a C₁-C₄ straight-chain or branched alkyl group, a C₂-C₄straight-chain or branched alkenyl group, a C₁-C₄ straight-chain orbranched haloalkyl group, or a C₂-C₄ straight-chain or branchedhaloalkenyl group, R¹⁵ represents a C₁-C₁₅ alkylene group or a C₂-C₁₅alkenylene group, and R¹⁶ represents a C₁-C₃ alkylene group;

[0034] compounds represented by the following formula (12):

[0035] wherein R⁷ and R⁸ independently represent a hydrogen atom, ahalogen atom, a C₁-C₄ straight-chain or branched alkyl group, a C₂-C₄straight-chain or branched alkenyl group, a C₁-C₄ straight-chain orbranched haloalkyl group, or a C₂-C₄ straight-chain or branchedhaloalkenyl group, R¹⁷ represents a C₁-C₁₅ alkylene group or a C₂-C₁₅alkenylene group, and R¹⁸ represents a C₁-C₃ alkylene group; and

[0036] compounds represented by the following formula (13):

[0037] wherein R⁷ and R⁸ independently represent a hydrogen atom, ahalogen atom, a C₁-C₄ straight-chain or branched alkyl group, a C₂-C₄straight-chain or branched alkenyl group, a C₁-C₄ straight-chain orbranched haloalkyl group, or a C₂-C₄ straight-chain or branchedhaloalkenyl group, and R¹⁹ and R²⁰ independently represent a hydrogenatom, a C₁-C₄ straight-chain or branched alkyl group, a C₂-C₄straight-chain or branched alkenyl group, a C₁-C₄ straight-chain orbranched haloalkyl group, a C₂-C₄ straight-chain or branched haloalkenylgroup, a hydroxyl group, a C₁-C₄ alkoxy group, an amino group, acarboxyl group, an ester group, a carbonyl group or a halogen atom.

[0038] As examples of the unsaturated compound of the above formula (9),there can be mentioned those which are represented by the followingformulae (14) through (20).

[0039] Compounds represented by the following formula (14):

[0040] wherein R⁷ and R⁸ independently represent a hydrogen atom, ahalogen atom, a C₁-C₄ straight-chain or branched alkyl group, a C₂-C₄straight-chain or, branched alkenyl group, a C₁-C₄ straight-chain orbranched haloalkyl group, or a C₂-C₄ straight-chain or branchedhaloalkenyl group, and R²¹ independently represents a C₁-C₄straight-chain or branched alkyl group, a C₂-C₄ straight-chain orbranched alkenyl group, a C₁-C₄ straight-chain or branched haloalkylgroup, a C₂-C₄ straight-chain or branched haloalkenyl group, a hydroxylgroup, a C₁-C₄ alkoxy group, an amino group, a carboxyl group, an estergroup, a carbonyl group or a halogen atom, and n is an integer in therange of 0 to 8;

[0041] compounds represented by the following formula (15):

[0042] wherein R⁷, R⁸ and R²¹ are the same as defined above for formula(14), and n is an integer in the range of 0 to 10;

[0043] compounds represented by the following formula (16):

[0044] wherein R⁷, R⁸ and R²¹ are the same as defined above for formula(14), and n is an integer in the range of 0 to 6;

[0045] compounds represented by the following formula (17):

[0046] wherein R⁷, R⁸ and R²¹ are the same as defined above for formula(14), and n is an integer in the range of 0 to 8;

[0047] compounds represented by the following formula (18):

[0048] wherein R⁷, R⁸ and R²¹ are the same as defined above for formula(14), and n is an integer in the range of 0 to 6;

[0049] compounds represented by the following formula (19):

[0050] wherein R⁷, R⁸ and R²¹ are the same as defined above for formula(14), and n is an integer in the range of 0 to 8; and

[0051] compounds represented by the following formula (20):

[0052] wherein R⁷, R⁸ and R²¹ are the same as defined above for formula(14), and n is an integer in the range of 0 to 8.

[0053] As examples of the unsaturated compound of the above formula(10), there can be mentioned those which are represented by thefollowing formulae (21) through (27).

[0054] Compounds represented by the following formula (21):

[0055] wherein R⁷ and R⁸ independently represent a hydrogen atom, ahalogen atom, a C₁-C₄ straight-chain or branched alkyl group, a C₂-C₄straight-chain or branched alkenyl group, a C₁-C₄ straight-chain orbranched haloalkyl group, or a C₂-C₄ straight-chain or branchedhaloalkenyl group, and R²¹ independently represents a C₁-C₄straight-chain or branched alkyl group, a C₂-C₄ straight-chain orbranched alkenyl group, a C₁-C₄ straight-chain or branched haloalkylgroup, a C₂-C₄ straight-chain or branched haloalkenyl group, a hydroxylgroup, a C₁-C₄ alkoxy group, an amino group, a carboxyl group, an estergroup, a carbonyl group or a halogen atom, and n is an integer in therange of 0 to 7;

[0056] compounds represented by the following formula (22):

[0057] wherein R⁷, R⁸ and R²¹ are the same as defined above for formula(21), and n is an integer in the range of 0 to 9;

[0058] compounds represented by the following formula (23):

[0059] wherein R⁷, R⁸ and R²¹ are the same as defined above for formula(21), and n is an integer in the range of 0 to 5;

[0060] compounds represented by the following formula (24):

[0061] wherein R⁷, R⁸ and R²¹ are the same as defined above for formula(21), and n is an integer in the range of 0 to 7;

[0062] compounds represented by the following formula (25):

[0063] wherein R⁷, R⁸ and R²¹ are the same as defined above for formula(21), and n is an integer in the range of 0 to 5;

[0064] compounds represented by the following formula (26):

[0065] wherein R⁷, R⁸ and R²¹ are the same as defined above for formula(21), and n is an integer in the range of 0 to 7; and

[0066] compounds represented by the following formula (27):

[0067] wherein R⁷, R⁸ and R²¹ are the same as defined above for formula(21), and n is an integer in the range of 0 to 7.

[0068] Among the unsaturated compounds of formula (22),1-ethylcyclohexene represented by the following formula (36) isespecially preferable.

[0069] As examples of the unsaturated compound of the above formula(11), there can be mentioned those which are represented by thefollowing formulae (28) through (31).

[0070] Compounds represented by the following formula (28):

[0071] wherein R⁷ and R⁸ independently represent a hydrogen atom, ahalogen atom, a C₁-C₄ straight-chain or branched alkyl group, a C₂-C₄straight-chain or branched alkenyl group, a C₁-C₄ straight-chain orbranched haloalkyl group, or a C₂-C₄ straight-chain or branchedhaloalkenyl group, and R²¹ independently represents a C₁-C₄straight-chain or branched alkyl group, a C₂-C₄ straight-chain orbranched alkenyl group, a C₁-C₄ straight-chain or branched haloalkylgroup, a C₂-C₄ straight-chain or branched haloalkenyl group, a hydroxylgroup, a C₁-C₄ alkoxy group, an amino group, a carboxyl group, an estergroup, a carbonyl group or a halogen atom, and n is an integer in therange of 0 to 8;

[0072] compounds represented by the following formula (29):

[0073] wherein R⁷, R⁸ and R²¹ are the same as defined above for formula(28), and n is an integer in the range of 0 to 8;

[0074] compounds represented by the following formula (30):

[0075] wherein R⁷, R⁸ and R²¹ are the same as defined above for formula(28), n is an integer in the range of 0 to 5, R²² independentlyrepresents a C₁-C₄ straight-chain or branched alkyl group, a C₂-C₄straight-chain or branched alkenyl group, a C₁-C₄ straight-chain orbranched haloalkyl group, a C₂-C₄ straight-chain or branched haloalkenylgroup, a hydroxyl group, a C₂-C₄ alkoxy group, an amino group, acarboxyl group, an ester group, a carbonyl group or a halogen atom, andm is an integer in the range of 0 to 8; and,

[0076] compounds represented by the following formula (31):

[0077] wherein R⁷, R⁸, R²¹ and R²² are the same as defined above forformulae (28) and (30), and n is an integer in the range of 0 to 5, andm is an integer in the range of 0 to 8.

[0078] As examples of the unsaturated compound of the above formula(12), there can be mentioned those which are represented by thefollowing formulae (32) through (35).

[0079] Compounds represented by the following formula (32):

[0080] wherein R⁷ and R⁸ independently represent a hydrogen atom, ahalogen atom, a C₁-C₄ straight-chain or branched alkyl group, a C₂-C₄straight-chain or branched alkenyl group, a C₁-C₄ straight-chain orbranched haloalkyl group, or a C₂-C₄ straight-chain or branchedhaloalkenyl group, and R²¹ independently represents a C₁-C₄straight-chain or branched alkyl group, a C₂-C₄ straight-chain orbranched alkenyl group, a C₁-C₄ straight-chain or branched haloalkylgroup, a C₂-C₄ straight-chain or branched haloalkenyl group, a hydroxylgroup, a C₁-C₄ alkoxy group, an amino group, a carboxyl group, an estergroup, a carbonyl group or a halogen atom, and n is an integer in therange of 0 to 8;

[0081] compounds represented by the following formula (33):

[0082] wherein R⁷, R⁸ and R²¹ are the same as defined above for formula(32), and n is an integer in the range of 0 to 8;

[0083] compounds represented by the following formula (34):

[0084] wherein R⁷, R⁸ and R²¹ are the same as defined above for formula(32), n is an integer in the range of 0 to 5, R²² independentlyrepresents a C₁-C₄ straight-chain or branched alkyl group, a C₂-C₄straight-chain or branched alkenyl group, a C₁-C₄ straight-chain orbranched haloalkyl group, a C₂-C₄ straight-chain or branched haloalkenylgroup, a hydroxyl group, a C₁-C₄ alkoxy group, an amino group, acarboxyl group, an ester group, a carbonyl group or a halogen atom, andm is an integer in the range of 0 to 8; and,

[0085] compounds represented by the following formula (35):

[0086] wherein R⁷, R⁸, R²¹ and R²² are the same as defined above forformulae (32) and (34), and n is an integer in the range of 0 to 8, andm is an integer in the range of 0 to 8.

[0087] Among the unsaturated compounds of formula (13),2-methyleneadamantane represented by the following formula (37) isespecially preferable.

[0088] In R⁷, R⁸ and R¹⁹ to R²² of the above formulae (7) to (35), theterms “C₁-C₄ straight-chain or branched haloalkyl group” and “C₂-C₄straight-chain or branched haloalkenyl group” mean a C₁-C₄straight-chain or branched alkyl group and a C₂-C₄ straight-chain orbranched alkenyl group, each having one or more halogen substituents,respectively. The halogen substituent includes chlorine, bromine, iodineand fluorine. The term “halogen atom” in R⁷, R⁸ and R¹⁹ to R²² of theformulae (7) to (35) means chlorine, bromine, iodine and fluorine atoms.

[0089] The unsaturated compounds of formulae (2) and (3) used in theprocess of the present invention can be easily prepared, for example, bya method wherein a commercially available corresponding tertiary alcoholis subjected to intramolecular dehydration reaction, or a method whereina commercially available corresponding carbonyl compound is subjected toWittig reaction.

[0090] The amount of the unsaturated compound of formula (2) or (3) usedin the process of the present invention is not particularly limited, butis preferably in the range of 1 mol to 20 mols per mol of the acrylicacid compound (1). When the amount of the unsaturated compound is toosmall, the conversion of the acrylic acid compound tends to be poor. Incontrast, when the amount of the unsaturated compound is too large, theproduction cost is liable to be increased because many unsaturatedcompounds including 2-methyleneadamantane are expensive.

[0091] When the acrylic acid compound of formula (1) is allowed to reactwith the unsaturated compound of formula (2) or (3) by the process ofthe present invention, the acrylate compound of formula (4) can beproduced with an enhanced efficiency. Especially when an acrylic acidcompound represented by the following formula (38):

[0092] wherein R⁶ is a hydrogen atom, a fluorine atom, an alkyl group(preferably a C₁-C₄ straight-chain or branched alkyl group), an alkenylgroup (preferably a C₂-C₄ straight-chain or branched alkenyl group), afluoroalkyl group (preferably a C₁-C₄ straight-chain or branchedfluoroalkyl group), or a fluoroalkenyl group (preferably a C₂-C₄straight-chain or branched fluoroalkenyl group), is allowed to reactwith 2-methyleneadamantane represented by the following formula (37):

[0093] a methyladamantyl acrylate compound represented by the followingformula (40) can be produced with greatly enhanced efficiency.

[0094] wherein R⁶ is the same as defined above for formula (38).

[0095] This makes a striking contrast with the conventional processwherein a methyladamantyl acrylate compound having a fluoroalkyl groupsuch as 2-methyl-2-adamantyl α-trifluoromethylacrylate (MAFAC) isproduced in a low yield.

[0096] The reaction of the acrylic acid compound of formula (1) with theunsaturated compound of formula (2) or (3) can be carried out in thepresence of a catalyst to more enhance the efficiency. The catalyst ispreferably an acidic catalyst, which includes, for example, hydrogenfluoride, hydrogen chloride, hydrogen bromide, hydrogen iodide, nitricacid, phosphoric acid, sulfonic acid compounds, carboxylic acidcompounds and Lewis acid compounds.

[0097] By the term “sulfonic acid compounds” used herein, we meancatalysts having a sulfonic acid group in the molecule structure. Thesulfonic acid compounds are not particularly limited provided that theyhave a sulfonic acid group, and, as specific examples thereof, there canbe mentioned inorganic sulfonic acids such as sulfuric acid,fluorosulfonic acid and chlorosulfonic acid; aliphatic sulfonic acidssuch as methanesulfonic acid, ethanesulfonic acid, propanesulfonic acid,allylsulfonic acid, butanesulfonic acid, pentanesulfonic acid,hexanesulfonic acid, heptanesulfonic acid, octanesulfonic acid,nonanesulfonic acid, decanesulfonic acid, dodecanesulfonic acid,tetradecanesulfonic acid and DL-camphor-10-sulfonic acid; substitutedaliphatic sulfonic acids such as trifluoromethanesulfonic acid,aminomethanesulfonic acid, 2-bromoethanesulfonic acid,2-(N-morpholino)ethanesulfonic acid,N,N′-bis(2-hydroxyethyl)-2-aminoethanesulfonic acid,N-(acetamido)-2-aminoethanesulfonic acid,N-2-hydroxyethylpiperazine-N′-2-ethanesulfonic acid,N-cyclohexyl-2-aminoethanesulfonic acid, 3-aminopropanesulfonic acid,N-cyclohexyl-2-hydroxy-3-aminopropanesulfonic acid,3-chloro-2-hydroxypropanesulfonic acid, 3-(N-morpholino)propanesulfonicacid, 2-hydroxy-3-morpholinopropanesulfonic acid,2-acrylamide-2-methylpropanesulfonic acid,2-amino-5-methylbenzene-1-sulfonic acid, methallylsulfonic acid andtaurine; aromatic sulfonic acids such as benzenesulfonic acid,p-chlorobenzenesulfonic acid, p-phenolsulfonic acid, guaiacol-4-sulfonicacid, p-styrenesulfonic acid, phenylhydrazine-p-sulfonic acid,1,2-benzenedisulfonic acid, 1,3-benzenedisulfonic acid,1,4-benzenedisulfonic acid, m-toluenesulfonic acid, p-toluenesulfonicacid, 2,4-dimethylbenzenesulfonic acid, 2,5-dimethylbenzenesulfonicacid, 2-mesitylenesulfonic acid, p-ethylbenzenesulfonic acid,3,5-dichloro-2-hydroxybenzenesulfonic acid,2,4,6-trinitrobenzenesulfonic acid, o-aminobenzenesulfonic acid,m-xylidine-6-sulfonic acid, 4-amino-2-methylbenzene-1-sulfonic acid,4-amino-5-methoxy-2-methylbenzenesulfonic acid,4-amino-2-chlorotoluene-5-sulfonic acid, 1-naphthalenesulfonic acid,2-naphthalenesulfonic acid, 2,6-naphthalenedisulfonic acid,2,7-naphthalenedisulfonic acid, 1-naphthol-2-sulfonic acid,1-naphthol-4-sulfonic acid, 1-naphthol-8-sulfonic acid,2-naphthol-6-sulfonic acid, 2-naphthol-3,6-disulfonic acid,1-naphthylamine-4-sulfonic acid, 1-naphthylamine-6-sulfonic acid,1-naphthylamine-8-sulfonic acid, 2-naphthylamine-1-sulfonic acid,2-naphthylamine-6-sulfonic acid, 2,3-dihydroxynaphthalene-6-sulfonicacid, 2-amino-5-naphthol-7-sulfonic acid,8-amino-1-naphthol-3,6-disulfonic acid,8-aminonaphthalene-1,3,6-trisulfonic acid,8-anilino-1-naphthalenesulfonic acid,4,4′-diaminostilbene-2,2′-disulfonic acid,7-iodo-8-hydroxyquinoline-5-sulfonic acid, diphenylamine-4-sulfonicacid, 1-pyrenesulfonic acid and sulfanilic acid; and sulfonic acid typecation-exchange resins such as Nafion (available from Du Pont Co.),sulfonic acid type Amberlist (available from Rohm & Haas Co.), sulfonicacid type Amberlite (available from Rohm & Haas Co.), sulfonic acid typeDiaion (available from Mitsubishi Chem. Corp.), sulfonic acid typeDuolite (available from Sumitomo Chem. Co.), sulfonic acid type Dowex(available from Dow Chem. Co.), sulfonic acid type Purolite (availablefrom Purolite Co.) and sulfonic acid type Lewatit (available from BayerAG).

[0098] By the term “carboxylic acid compounds” used herein, we meancatalysts having a carboxylic acid group in the molecule structure. Thecarboxylic acid compounds are not particularly limited provided thatthey have a carboxylic acid group, and, as specific examples thereof,there can be mentioned aliphatic carboxylic acids such as formic acid,acetic acid, propionic acid, butyric acid, valeric acid, caproic acid,heptanoic acid, caprylic acid, pelargonic acid, capric acid,n-undecylenic acid, acrylic acid, crotonic acid, isocrotonic acid,vinylacetic acid, methacrylic acid, angelic acid, tiglic acid,2-pentenoic acid, 3-pentenoic acid, 4-pentenoic acid, α-ethylacrylicacid, β,β-dimethylacrylic acid, 2-hexenoic acid, 3-hexenoic acid,4-hexenoic acid, 5-hexenoic acid, 2-methyl-2-pentenoic acid,3-methyl-2-pentenoic acid, 4-methyl-2-pentenoic acid,4-methyl-3-pentenoic acid, 2-heptenoic acid, 2-octenoic acid, 4-decenoicacid, 9-decenoic acid, 9-undecenoic acid, 10-undecenoic acid,4-dodecenoic acid, 5-dodecenoic acid, propiolic acid, tetrolic acid,ethylpropiolic acid, n-propylpropiolic acid, isopropylpropiolic acid,n-butylpropiolic acid, t-butylpropiolic acid, n-amylpropiolic acid,9-undecynoic acid, 2,4-pentadienoic acid, 2,4-hexadienoic acid,fluoroacetic acid, difluoroacetic acid, trifluoroacetic acid,chloroacetic acid, dichloroacetic acid, trichloroacetic acid,bromoacetic acid, dibromoacetic acid, tribromoacetic acid, iodoaceticacid, diiodoacetic acid, triiodoacetic acid, α-chloropropionic acid,β-chloropropionic acid, α-bromopropionic acid, β-bromopropionic acid,α-iodopropionic acid, β-iodopropionic acid, α-chloroacrylic acid,β-chloroacrylic acid, trichloroacrylic acid, α-bromoacrylic acid,β-bromoacrylic acid, α-iodoacrylic acid, β-iodoacrylic acid,α-chlorocrotonic acid, β-chlorocrotonic acid, γ-chlorocrotonic acid,α-bromocrotonic acid, β-bromocrotonic acid, γ-bromocrotonic acid, oxalicacid, malonic acid, succinic acid, glutaric acid, adipic acid, pimelicacid, suberic acid, azelaic acid, sebacic acid, chloromalonic acid,dichloromalonic acid, bromomalonic acid, dibromomalonic acid,chlorosuccnic acid, dichlorosuccnic acid, bromosuccnic acid,dibromosuccnic acid, methylsuccnic acid, methylenemalonic acid,α-methylglutaric acid, β-methylglutaric acid, maleic acid, fumaric acid,itaconic acid, citraconic acid, mesaconic acid, glutaconic acid,trans-transmuconic acid, cis-cismuconic acid, cis-transmuconic acid,acetylenedicarboxylic acid, 1-propylene-1,3-dicarboxylic acid,1-butyne-1,4-dicarboxylic acid, 2-butyne-1,4-dicarboxylic acid,propane-1,2,3-tricarboxylic acid and butane-1,2,3,4-tetracarboxylicacid; and aromatic carboxylic acids such as benzoic acid,o-hydroxybenzoic acid, m-hydroxybenzoic acid, p-hydroxybenzoic acid,4-acetylbenzoic acid, o-fluorobenzoic acid, phthalic acid,1,2,4,5-benzenetetracarboxylic acid, 1-naphthoic acid, 2-naphthoic acid,3-hydroxy-2-naphthoic acid, 4-biphenylcarboxylic acid,4,4′-biphenyldicarboxylic acid, 9-anthracenedicarboxylic acid,2-quinolinecarboxylic acid and 4-pyridinecarboxylic acid.

[0099] As specific examples of the Lewis acid compounds used as acatalyst in the present invention, there can be mentioned borontrifluoride, boron trichloride, boron tribromide, aluminum chloride,aluminum bromide, iron(III) chloride, iron(III) bromide, antimonytrichloride, antimony pentachloride, titanium trichloride, titaniumtetrachloride, zinc chloride, zinc bromide, tin chloride, copperchloride, tungsten chloride, iron powder and zeolites.

[0100] Among the above-recited catalysts, sulfonic acid compounds suchas sulfuric acid and p-toluenesulfonic acid are preferable. Sulfuricacid is especially preferable in view of safety and cost.

[0101] The catalysts may be used either alone or as a mixture of atleast two thereof.

[0102] The amount of the catalyst is not particularly limited, but isusually in the range of 10⁻⁴ mol to 1 mol per mol of the acrylic acidcompound of formula (1).

[0103] In a preferable example of the process of the present invention,an acrylate compound represented by the following formula (41):

[0104] wherein R⁶ is a hydrogen atom, a methyl group or atrifluoromethyl group, and R²³ is 2-methyl-2-adamanthyl group or a1-methylcyclohexyl group, is produced by allowing an acrylic acidcompound represented by the following formula (38):

[0105] wherein R⁶ is the same as defined above for formula (41), toreact with 2-methyleneadamantane or 1-ethylcyclohexene, represented bythe following formula (37) or (36), respectively:

[0106] in the presence of an acid catalyst comprised of sulfuric acid orp-toluenesulfonic acid.

[0107] The reaction temperature is not particularly limited, but isusually in the range of −50° C. to 100° C.

[0108] The process of the present invention can be carried out in thepresence of a solvent. The solvent used is not particularly limited,and, as specific examples thereof, there can be mentioned aliphatichydrocarbons such as hexane and heptane; aromatic hydrocarbons such asbenzene, toluene and xylene; halogenated hydrocarbons such asdichloromethane and dichloroethane; and ethers such as diethyl ether andtetrahydrofuran.

[0109] After completion of the reaction, the residual raw materials andcatalyst are removed, for example, by washing a reaction mixture withwater, and the object acrylate compound can be obtained by conventionalpurification procedures such as distillation, recrystallization andcolumn chromatography.

[0110] The invention will now be specifically described by the followingexamples that by no means limit the scope of the invention.

REFERENCE EXAMPLE 1 Synthesis of 2-methyleneadamantane

[0111] One liter flask equipped with a Dean-Stark condenser was chargedwith 166.3 g (1.0 mol) of 2-methyl-2-adamantanol (supplied bySigma-Aldrich Co.), 2.0 g (20 mmol) of sulfuric acid and 500 g oftoluene. The content was heated to the solvent reflux temperature. Whiletoluene and water produced through the reaction were collected as anazeotrope by the Dean-Stark condenser, the reaction mixture was refluxedfor 2 hours. After completion of the reaction, the catalyst was removedby washing the reaction mixture with water and the obtained organicphase was concentrated to dryness to give 152.5 g of white solid2-methyleneadamantane (purity: 99.0%, yield: 98.0%).

EXAMPLE 1 Synthesis of 2-methyl-2-adamantyl α-trifluoromethylacrylate[MAFAC]

[0112] A 500 ml flask was flushed with nitrogen to displace the air withnitrogen, and was charged with 70.0 g (0.50 mol) ofα-trifluoromethylacrylic acid (supplied from Tosoh F-tech Inc.), 1.0 g(10 mmol) of sulfuric acid and 100 g of toluene. Separately 88.8 g (0.60mol) of 2-methyleneadamantane, prepared by the same procedures asdescribed in Reference Example 1, was dissolved in 100 g of toluene. Theobtained solution of 2-methyleneadamantane in toluene was dropwise addedto the content in the flask over a period of about 3 hours, while thecontent was maintained at a reaction temperature of about 5° C. Then thecontent was stirred for 15 hours at the same temperature. Aftercompletion of the reaction, the residual catalyst was neutralized byadding 40.0 g (50 mmol) of a 5% aqueous sodium hydroxide solution, andthe neutralized liquid was washed with an aqueous saturated sodiumchloride solution. The thus-obtained organic phase was subjected tocolumn chromatography, and further, analyzed by NMR and massspectrometry. Thus, 133.9 g (yield: 93.0%) of the object2-methyl-2-adamantyl α-trifluoromethylacrylate was obtained.

[0113] Results of Analysis:

[0114] (1) ¹H-NMR (CDCl₃): δ(ppm)=6.73(1H,S), 6.42(1H,S),1.63-2.43(15H,m)

[0115] (2) MS spectrum (m/z): 288(M+)

EXAMPLE 2 Synthesis of 2-methyl-2-adamantyl Acrylate [MAAC]

[0116] A 500 ml flask was flushed with nitrogen to displace the air withnitrogen, and was charged with 36.0 g (0.50 mol) of acrylic acid, 0.5 g(5 mmol) of sulfuric acid and 100 g of toluene. Separately 88.8 g (0.60mol) of 2-methyleneadamantane, prepared by the same procedures asdescribed in Reference Example 1, was dissolved in 100 g of toluene. Theobtained solution of 2-methyleneadamantane in toluene was dropwise addedto the content in the flask over a period of about 3 hours, while thecontent was maintained at a reaction temperature of about 20° C. Thenthe content was stirred for 5 hours at the same temperature. Aftercompletion of the reaction, the residual catalyst was neutralized byadding 40.0 g (50 mmol) of a 5% aqueous sodium hydroxide solution, andthe neutralized liquid was washed with an aqueous saturated sodiumchloride solution. The thus-obtained organic phase was subjected tocolumn chromatography, and further, analyzed by NMR and massspectrometry. Thus, 100.7 g (yield: 91.5%) of the object2-methyl-2-adamantyl acrylate was obtained.

EXAMPLE 3 Synthesis of 2-methyl-2-adamantyl Methacrylate [MAMC]

[0117] A 500 ml flask was flushed with nitrogen to displace the air withnitrogen, and was charged with 43.0 g (0.50 mol) of methacrylic acid,0.95 g (5 mmol) of p-toluenesulfonic acid monohydrate (supplied by WakoPure Chem. Ind. Ltd.) and 100 g of toluene. Separately 74.0 g (0.50 mol)of 2-methyleneadamantane, prepared by the same procedures as describedin Reference Example 1, was dissolved in 100 g of toluene. The obtainedsolution of 2-methyleneadamantane in toluene was dropwise added to thecontent in the flask over a period of about 3 hours, while the contentwas maintained at a reaction temperature of about 5° C. Then the contentwas stirred for 5 hours at the same temperature. After completion of thereaction, the residual catalyst was neutralized by adding 40.0 g (50mmol) of a 5% aqueous sodium hydroxide solution, and the neutralizedliquid was washed with an aqueous saturated sodium chloride solution.The thus-obtained organic phase was subjected to column chromatography,and further, analyzed by NMR and mass spectrometry. Thus, 106.2 g(yield: 90.8%) of the object 2-methyl-2-adamantyl methacrylate wasobtained.

REFERENCE EXAMPLE 2 Synthesis of 1-ethylcyclohexanol

[0118] One liter flask was flushed with nitrogen to displace the airwith nitrogen, and was charged with 26.7 g (1.1 mol) of metallicmagnesium (supplied by Aldrich Co.) and 500 g of tetrahydrofuran. Among109.0 g (1.0 mol) of ethyl bromide (supplied by Kanto Chem. Co.), about5 g thereof was added to the content in the flask to confirm heatgeneration due to initiation of the exothermic Grignard reaction, andthen the remainder of ethyl bromide was dropwise added over a period ofabout 1 hour while the inner temperature was controlled so as not toexceed 50° C. Further, the reaction mixture was stirred at the sametemperature for 1 hour. Then, 98.2 g (1.0 mol) of cyclohexanone wasdropwise added over a period of about 3 hours while the reactiontemperature was controlled so as not to exceed 20° C. Further, thereaction mixture was stirred at the same temperature for 1 hour. Aftercompletion of the reaction, the reaction mixture was treated with 550 g(1.5 mol) of an aqueous HCl solution and the obtained organic phase wasconcentrated to dryness to give 127.6 g of a white solid. NMR and massspectroscopy of the white solid revealed that it was 1-ethylcyclohexanol(purity: 98.5%, yield: 98.0%).

REFERENCE EXAMPLE 3 Synthesis of 1-ethylcyclohexene

[0119] One liter flask equipped with a Dean-Stark condenser was chargedwith 64.1 g (0.5 mol) of 1-ethylcyclohexanol, prepared in ReferenceExample 2, 1.0 g (10 mmol) of sulfuric acid and 300 g of toluene. Thecontent was heated to the solvent reflux temperature. While toluene andwater produced through the reaction were collected as an azeotrope bythe Dean-Stark condenser, the reaction mixture was refluxed for 1 hours.After completion of the reaction, the catalyst was removed by washingthe reaction mixture with water and the obtained organic phase wasdistilled under reduced pressure to obtain 58.3 g of colorless liquid asa fraction of 77° C./15 kPa. NMR and mass spectroscopy of the colorlessliquid revealed that it was 1-ethylcyclohexene (purity: 96.0%, yield:87.5%).

EXAMPLE 4 Synthesis of 1-ethylcyclohexyl Methacrylate

[0120] A 500 ml flask was flushed with nitrogen to displace the air withnitrogen, and was charged with 43.0 g (0.5 mol) of methacrylic acid, 0.5g (5 mmol) of sulfuric acid and 100 g of toluene. Separately 110.2 g(1.0 mol) of 1-ethylcyclohexene, prepared by the same procedures asdescribed in Reference Example 3, was dissolved in 100 g of toluene. Theobtained solution of 1-ethylcyclohexene in toluene was dropwise added tothe content in the flask over a period of about 3 hours, while thecontent was maintained at a reaction temperature of about 30° C. Thenthe content was stirred for 15 hours at the same temperature. Aftercompletion of the reaction, the residual catalyst was neutralized byadding 40.0 g (50 mmol) of a 5% aqueous sodium hydroxide solution, andthe neutralized liquid was washed with an aqueous saturated sodiumchloride solution. The thus-obtained organic phase was subjected tocolumn chromatography, and further, analyzed by NMR and massspectrometry. Thus, 68.6 g (yield: 69.9%) of the object1-ethylcyclohexyl methacrylate was obtained.

[0121] Results of Analysis:

[0122] (1) ¹H-NMR (CDCl₃): δ(ppm)=6.12(1H,S), 5.55(1H,S),1.25-2.37(15H,m), 0.89(3H,t)

[0123] (2) MS spectrum (m/z): 196(M+)

COMPARATIVE EXAMPLE 1 Synthesis of 2-methyl-2-adamantylα-trifluoromethylacrylate [MAFAC] from 2-methyl-2-adamantanol andα-trifluoromethylacryloyl Chloride

[0124] A 500 ml flask was flushed with nitrogen to displace the air withnitrogen, and was charged with 83.1 g (0.50 mol) of2-methyl-2-adamantanol, 101.2 g (1.0 mol) of triethylamine and 200 g oftetrahydrofuran. Then 118.9 g (0.75 mol) of α-trifluoromethylacryloylchloride was dropwise added to the content in the flask over a period ofabout 1 hour, while the content was maintained at a reaction temperatureof about 0° C. Then the content was stirred for 10 hours at roomtemperature. After completion of the reaction, the reaction mixture waswashed with water and then with an aqueous saturated sodium chloridesolution. The thus-obtained organic phase was subjected to columnchromatography, and further, analyzed by NMR and mass spectrometry.Thus, 101.2 g (yield: 70.3%) of the object 2-methyl-2-adamantylα-trifluoromethylacrylate was obtained.

What is claimed is:
 1. A process for preparing an acrylate compoundrepresented by the following formula (4):

wherein R¹ and R² independently represent a hydrogen atom or a fluorineatom, R³ represents a hydrogen atom, a fluorine atom, an alkyl group, analkenyl group, a fluoroalkyl group or a fluoroalkenyl group, R⁴ and R⁵independently represent a hydrogen atom, a halogen atom, an alkyl group,an alkenyl group, a halogenated alkyl group, or a halogenated alkenylgroup; and X and Y independently represent a hydrocarbon group, whichmay have at least one substituent selected from the group consisting ofa halogen-containing substituent, an oxygen-containing substituent and anitrogen-containing substituent, and dashed line - - - - - means that Xand Y may be bonded together to form a cyclic structure; which comprisesallowing an acrylic acid compound represented by the following formula(1):

wherein R¹, R² and R³ are the same as defined above for formula (4), toreact with an unsaturated compound represented by the following formula(2) or (3):

wherein R⁴, R⁵, X and Y are the same as defined above for formula (4).2. The process according to claim 1, wherein the acrylic acid compoundis represented by the following formula (5):

wherein R¹ and R² independently represent a hydrogen atom or a fluorineatom, and R³ represents a hydrogen atom, a fluorine atom, a C₁-C₄straight-chain or branched alkyl group, a C₂-C₄ straight-chain orbranched alkenyl group, a C₁-C₄ straight-chain or branched fluoroalkylgroup, or a C₂-C₄ straight-chain or branched fluoroalkenyl group.
 3. Theprocess according to claim 1, wherein the acrylic acid compound isrepresented by the following formula (6):

wherein R³ represents a hydrogen atom, a fluorine atom, a C₁-C₄straight-chain or branched alkyl group, a C₂-C₄ straight-chain orbranched alkenyl group, a C₁-C₄ straight-chain or branched fluoroalkylgroup, or a C₂-C₄ straight-chain or branched fluoroalkenyl group.
 4. Theprocess according to claim 1, wherein the acrylic acid compound isselected from the group consisting of α-trifluoromethylacrylic acid,α-trifluoroethylacrylic acid, α-perfluoroethylacrylic acid,α-perfluoropropylacrylic acid, α-perfluorobutylacrylic acid,α-fluoroacrylic acid, acrylic acid and methacrylic acid.
 5. The processaccording to claim 1, wherein the acrylic acid compound is selected fromthe group consisting of α-trifluoromethylacrylic acid, acrylic acid andmethacrylic acid.
 6. The process according to any one of claims 1 to 5,wherein the unsaturated compound of formula (2) or (3) is selected fromthe group consisting of: a compound represented by the following formula(7):

wherein R⁷ and R⁸ independently represent a hydrogen atom, a halogenatom, a C₁-C₄ straight-chain or branched alkyl group, a C₂-C₄straight-chain or branched alkenyl group, a C₁-C₄ straight-chain orbranched haloalkyl group, or a C₂-C₄ straight-chain or branchedhaloalkenyl group, and R⁹ and R¹⁰ independently represent a C₁-C₁₀straight-chain or branched alkyl group, or a C₂-C₁₀ straight-chain orbranched alkenyl group; a compound represented by the following formula(8):

wherein R⁷ and R⁸ independently represent a hydrogen atom, a halogenatom, a C₁-C₄ straight-chain or branched alkyl group, a C₂-C₄straight-chain or branched alkenyl group, a C₁-C₄ straight-chain orbranched haloalkyl group, or a C₂-C₄ straight-chain or branchedhaloalkenyl group, and R¹¹ and R¹² independently represent a C₁-C₁₀straight-chain or branched alkyl group, or a C₂-C₁₀ straight-chain orbranched alkenyl group; a compound represented by the following formula(9):

wherein R⁷ and R⁸ independently represent a hydrogen atom, a halogenatom, a C₁-C₄ straight-chain or branched alkyl group, a C₂-C₄straight-chain or branched alkenyl group, a C₁-C₄ straight-chain orbranched haloalkyl group, or a C₂-C₄ straight-chain or branchedhaloalkenyl group, and R¹³ represents a C₂-C₁₅ straight-chain orbranched alkylene group or a C₂-C₁₅ straight-chain or branchedalkenylene group; a compound represented by the following formula (10):

wherein R⁷ and R⁸ independently represent a hydrogen atom, a halogenatom, a C₁-C₄ straight-chain or branched alkyl group, a C₂-C₄straight-chain or branched alkenyl group, a C₁-C₄ straight-chain orbranched haloalkyl group, or a C₂-C₄ straight-chain or branchedhaloalkenyl group, and R¹⁴ represents a C₁-C₁₅ alkylene group, or aC₂-C₁₅ alkenylene group; a compound represented by the following formula(11):

wherein R⁷ and R⁸ independently represent a hydrogen atom, a halogenatom, a C₁-C₄ straight-chain or branched alkyl group, a C₂-C₄straight-chain or branched alkenyl group, a C₁-C₄ straight-chain orbranched haloalkyl group, or a C₂-C₄ straight-chain or branchedhaloalkenyl group, R¹⁵ represents a C₁-C₁₅ alkylene group or a C₂-C₁₅alkenylene group, and R¹⁶ represents a C₁-C₃ alkylene group; a compoundrepresented by the following formula (12):

wherein R⁷ and R⁸ independently represent a hydrogen atom, a halogenatom, a C₁-C₄ straight-chain or branched alkyl group, a C₂-C₄straight-chain or branched alkenyl group, a C₁-C₄ straight-chain orbranched haloalkyl group, or a C₂-C₄ straight-chain or branchedhaloalkenyl group, R¹⁷ represents a C₁-C₁₅ alkylene group or a C₂-C₁₅alkenylene group, and R¹⁸ represents a C₁-C₃ alkylene group; and acompound represented by the following formula (13):

wherein R⁷ and R⁸ independently represent a hydrogen atom, a halogenatom, a C₁-C₄ straight-chain or branched alkyl group, a C₂-C₄straight-chain or branched alkenyl group, a C₁-C₄ straight-chain orbranched haloalkyl group, or a C₂-C₄ straight-chain or branchedhaloalkenyl group, and R¹⁹ and R²⁰ independently represent a hydrogenatom, a C₁-C₄ straight-chain or branched alkyl group, a C₂-C₄straight-chain or branched alkenyl group, a C₁-C₄ straight-chain orbranched haloalkyl group, a C₂-C₄ straight-chain or branched haloalkenylgroup, a hydroxyl group, a C₁-C₄ alkoxy group, an amino group, acarboxyl group, an ester group, a carbonyl group or a halogen atom. 7.The process according to claim 6, wherein the unsaturated compound offormulae (9) is selected from the group consisting of: a compoundrepresented by the following formula (14):

wherein R⁷ and R⁸ independently represent a hydrogen atom, a halogenatom, a C₁-C₄ straight-chain or branched alkyl group, a C₂-C₄straight-chain or branched alkenyl group, a C₁-C₄ straight-chain orbranched haloalkyl group, or a C₂-C₄ straight-chain or branchedhaloalkenyl group, and R²¹ independently represents a C₁-C₄straight-chain or branched alkyl group, a C₂-C₄ straight-chain orbranched alkenyl group, a C₁-C₄ straight-chain or branched haloalkylgroup, a C₂-C₄ straight-chain or branched haloalkenyl group, a hydroxylgroup, a C₁-C₄ alkoxy group, an amino group, a carboxyl group, an estergroup, a carbonyl group or a halogen atom, and n is an integer in therange of 0 to 8; a compound represented by the following formula (15):

wherein R⁷, R⁸ and R²¹ are the same as defined above for formula (14),and n is an integer in the range of 0 to 10; a compound represented bythe following formula (16):

wherein R⁷, R⁸ and R²¹ are the same as defined above for formula (14),and n is an integer in the range of 0 to 6; a compound represented bythe following formula (17):

wherein R⁷, R⁸ and R²¹ are the same as defined above for formula (14),and n is an integer in the range of 0 to 8; a compound represented bythe following formula (18):

wherein R⁷, R⁸ and R²¹ are the same as defined above for formula (14),and n is an integer in the range of 0 to 6; a compound represented bythe following formula (19):

wherein R⁷, R⁸ and R²¹ are the same as defined above for formula (14),and n is an integer in the range of 0 to 8; and a compound representedby the following formula (20):

wherein R⁷, R⁸ and R²¹ are the same as defined above for formula (14),and n is an integer in the range of 0 to
 8. 8. The process according toclaim 6, wherein the unsaturated compound of formula (10) is selectedfrom the group consisting of: a compound represented by the followingformula (21):

wherein R⁷ and R⁸ independently represent a hydrogen atom, a halogenatom, a C₁-C₄ straight-chain or branched alkyl group, a C₂-C₄straight-chain or branched alkenyl group, a C₁-C₄ straight-chain orbranched haloalkyl group, or a C₂-C₄ straight-chain or branchedhaloalkenyl group, and R²¹ independently represents a C₁-C₄straight-chain or branched alkyl group, a C₂-C₄ straight-chain orbranched alkenyl group, a C₁-C₄ straight-chain or branched haloalkylgroup, a C₂-C₄ straight-chain or branched haloalkenyl group, a hydroxylgroup, a C₁-C₄ alkoxy group, an amino group, a carboxyl group, an estergroup, a carbonyl group or a halogen atom, and n is an integer in therange of 0 to 7; a compound represented by the following formula (22):

wherein R⁷, R⁸ and R²¹ are the same as defined above for formula (21),and n is an integer in the range of 0 to 9; a compound represented bythe following formula (23):

wherein R⁷, R⁸ and R²¹ are the same as defined above for formula (21),and n is an integer in the range of 0 to 5; a compound represented bythe following formula (24):

wherein R⁷, R⁸ and R²¹ are the same as defined above for formula (21),and n is an integer in the range of 0 to 7; a compound represented bythe following formula (25):

wherein R⁷, R⁸ and R²¹ are the same as defined above for formula (21),and n is an integer in the range of 0 to 5; a compound represented bythe following formula (26):

wherein R⁷, R⁸ and R²¹ are the same as defined above for formula (21),and n is an integer in the range of 0 to 7; and a compound representedby the following formula (27):

wherein R⁷, R⁸ and R²¹ are the same as defined above for formula (21),and n is an integer in the range of 0 to
 7. 9. The process according toclaim 6, wherein the unsaturated compound of formula (11) is selectedfrom the group consisting of: a compound represented by the followingformula (28):

wherein R⁷ and R⁸ independently represent a hydrogen atom, a halogenatom, a C₁-C₄ straight-chain or branched alkyl group, a C₂-C₄straight-chain or branched alkenyl group, a C₁-C₄ straight-chain orbranched haloalkyl group, or a C₂-C₄ straight-chain or branchedhaloalkenyl group, and R²¹ independently represents a C₁-C₄straight-chain or branched alkyl group, a C₂-C₄ straight-chain orbranched alkenyl group, a C₁-C₄ straight-chain or branched haloalkylgroup, a C₂-C₄ straight-chain or branched haloalkenyl group, a hydroxylgroup, a C₁-C₄ alkoxy group, an amino group, a carboxyl group, an estergroup, a carbonyl group or a halogen atom, and n is an integer in therange of 0 to 8; a compound represented by the following formula (29):

wherein R⁷, R⁸ and R²¹ are the same as defined above for formula (28),and n is an integer in the range of 0 to 8; a compound represented bythe following formula (30):

wherein R⁷, R⁸ and R²¹ are the same as defined above for formula (28), nis an integer in the range of 0 to 5, R²² independently represents aC₁-C₄ straight-chain or branched alkyl group, a C₂-C₄ straight-chain orbranched alkenyl group, a C₁-C₄ straight-chain or branched haloalkylgroup, a C₂-C₄ straight-chain or branched haloalkenyl group, a hydroxylgroup, a C₁-C₄ alkoxy group, an amino group, a carboxyl group, an estergroup, a carbonyl group or a halogen atom, and m is an integer in therange of 0 to 8; and a compound represented by the following formula(31):

wherein R⁷, R⁸, R²¹ and R²² are the same as defined above for formulae(28) and (30), and n is an integer in the range of 0 to 5, and m is aninteger in the range of 0 to
 8. 10. The process according to claim 6,wherein the unsaturated compound of formula (12) is selected from thegroup consisting of: a compound represented by the following formula(32):

wherein R⁷ and R⁸ independently represent a hydrogen atom, a halogenatom, a C₁-C₄ straight-chain or branched alkyl group, a C₂-C₄straight-chain or branched alkenyl group, a C₁-C₄ straight-chain orbranched haloalkyl group, or a C₂-C₄ straight-chain or branchedhaloalkenyl group, and R²¹ independently represents a C₁-C₄straight-chain or branched alkyl group, a C₂-C₄ straight-chain orbranched alkenyl group, a C₁-C₄ straight-chain or branched haloalkylgroup, a C₂-C₄ straight-chain or branched haloalkenyl group, a hydroxylgroup, a C₁-C₄ alkoxy group, an amino group, a carboxyl group, an estergroup, a carbonyl group or a halogen atom, and n is an integer in therange of 0 to 8; a compound represented by the following formula (33):

wherein R⁷, R⁸ and R²¹ are the same as defined above for formula (32),and n is an integer in the range of 0 to 8; a compound represented bythe following formula (34):

wherein R⁷, R⁸ and R²¹ are the same as defined above for formula (32), nis an integer in the range of 0 to 5, R²² independently represents aC₁-C₄ straight-chain or branched alkyl group, a C₂-C₄ straight-chain orbranched alkenyl group, a C₁-C₄ straight-chain or branched haloalkylgroup, a C₂-C₄ straight-chain or branched haloalkenyl group, a hydroxylgroup, a C₁-C₄ alkoxy group, an amino group, a carboxyl group, an estergroup, a carbonyl group or a halogen atom, and m is an integer in therange of 0 to 8; and a compound represented by the following formula(35):

wherein R⁷, R⁸, R²¹ and R²² are the same as defined above for formulae(32) and (34), and n is an integer in the range of 0 to 8, and m is aninteger in the range of 0 to
 8. 11. The process according to any one ofclaims 1 to 5, wherein the unsaturated compound of formula (3) is1-ethylcyclohexene represented by the following formula (36):

and the unsaturated compound of formula (2) is 2-methyleneadamantanerepresented by the following formula (37):


12. The process according to any one of claims 1 to 11, wherein thereaction of the acrylic acid compound of formula (1) with theunsaturated compound of formula (2) or (3) is carried out in thepresence of a catalyst.
 13. The process according to claim 12, whereinthe catalyst is an acidic catalyst.
 14. The process according to claim13, wherein the acidic catalyst is a sulfonic acid group-containingcatalyst.
 15. The process according to claim 14, wherein the sulfonicacid group-containing catalyst is sulfuric acid.
 16. A process forpreparing a methyladamantyl acrylate represented by the followingformula (40):

wherein R⁶ is a hydrogen atom, an alkyl group or a fluoroalkyl group,which comprises allowing an acrylic acid compound represented by thefollowing formula (38):

wherein R⁶ is the same as defined above for formula (40), to react with2-methyleneadamantane represented by the following formula (37):


17. The process according to claim 16, wherein the acrylic acid compoundis represented by the following formula (39):

wherein R⁶ represents a hydrogen atom, a C₁-C₄ straight-chain orbranched alkyl group, a C₂-C₄ straight-chain or branched alkenyl group,a C₁-C₄ straight-chain or branched fluoroalkyl group, or a C₂-C₄straight-chain or branched fluoroalkenyl group.
 18. The processaccording to claim 16, wherein the acrylic acid compound is selectedfrom the group consisting of α-trifluoromethylacrylic acid, acrylic acidand methacrylic acid.
 19. A process for preparing an acrylate compoundrepresented by the following formula (41):

wherein R⁶ is a hydrogen atom, a methyl group or a trifluoromethylgroup, and R²³ is 2-methyl-2-adamanthyl group or a 1-ethylcyclohexylgroup, which comprises allowing an acrylic acid compound represented bythe following formula (38):

wherein R⁶ is the same as defined above for formula (41), to react with2-methyleneadamantane or 1-ethylcyclohexene, represented by thefollowing formula (37) or (36), respectively:

in the presence of an acid catalyst comprised of sulfuric acid orp-toluenesulfonic acid.